EP0481287B1 - Procédé pour la fabrication de cyclohexylidenebisphénols substitués - Google Patents

Procédé pour la fabrication de cyclohexylidenebisphénols substitués Download PDF

Info

Publication number
EP0481287B1
EP0481287B1 EP91116809A EP91116809A EP0481287B1 EP 0481287 B1 EP0481287 B1 EP 0481287B1 EP 91116809 A EP91116809 A EP 91116809A EP 91116809 A EP91116809 A EP 91116809A EP 0481287 B1 EP0481287 B1 EP 0481287B1
Authority
EP
European Patent Office
Prior art keywords
formula
phenol
mol
acidic
iii
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91116809A
Other languages
German (de)
English (en)
Other versions
EP0481287A3 (en
EP0481287A2 (fr
Inventor
Volker Dr. Serini
Klaus D. Dr. Berg
Alfred Dr. Eitel
Carl Dr. Casser
Helmut Dr. Waldmann
Manfred Dr. Hajek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0481287A2 publication Critical patent/EP0481287A2/fr
Publication of EP0481287A3 publication Critical patent/EP0481287A3/de
Application granted granted Critical
Publication of EP0481287B1 publication Critical patent/EP0481287B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the invention relates to a process for the preparation of cyclohexylidene bisphenols from phenols in the presence of ion exchange resins and special cyclohexanones.
  • the cyclohexylidene bisphenols produced according to the invention are valuable intermediates for the preparation of polycondensation products.
  • they are suitable for the production of polyether ketones, polyether sulfones, aromatic polyesters, aromatic polyester carbonates and polycarbonates, which are distinguished by a high glass transition temperature, particularly good demolding behavior, exceptionally good melt flowability, especially taking into account the high glass transition temperature and very good UV, heat and hydrolysis stability award.
  • cyclohexylidene bisphenols are known, for example from US Pat. Nos. 2,069,573, 2,894,004, 1,760,758, 2,538,725, 2,069,560, FR-A 1,559,848, GB-A 1 449 207, JP-A 1 268-640, J. Am. Chem. Soc. 61 , 345 (1939). They are produced in the presence of hydrogen chloride or sulfuric acid as a condensation catalyst. Sulfur compounds; For example, n-butyl mercaptan can be added.
  • a disadvantage when working with hydrogen chloride is its high corrosiveness. Corrosion-resistant equipment is therefore required for large-scale production, which significantly increases the production costs of the bisphenols of the formula (I).
  • the corrosiveness of the HCl-containing reaction mixtures is increased by adding water during the workup. The HCl-containing aqueous solutions thus obtained are difficult to work up. If the reaction solutions are processed with bases, e.g. Neutralized sodium hydroxide solution, aqueous, phenol-containing saline solutions are also formed.
  • Suitable phenols of the formula (II) are, for example, phenol, 2,6-dimethylphenol, 2-chlorophenol, 2,6-dichlorophenol, 2-methylphenol, 2-bromophenol, 2-tert-butylphenol, 2-phenylphenol.
  • Suitable cyclohexanones of the formula (III) are, for example, 3-methylcyclohexanone, 4-methylcyclohexanone, 3,5-dimethylcyclohexanone, 3-tert-butylcyclohexanone, 3,5-di-tert.-butylcyclohexanone, 3-phenylcyclohexanone, 4-phenylcyclohexanone, 4 -Cyclohexylcyclohexanone, 4-tert-butylcyclohexanone.
  • phenol of the formula (II) is used in a stoichiometric excess to cyclohexanone of the formula (III).
  • a stoichiometric excess to cyclohexanone of the formula (III) Preferably 3 to 30 moles of phenol are used per mole of ketone.
  • a molar ratio of phenol to cyclohexanone of 6: 1 to 25: 1 is particularly preferred.
  • sulfonated styrene-divinylbenzene resins sulfonated crosslinked styrene polymers and phenol-formaldehyde sulfonic acid resins are used as acidic condensation catalysts. These are available under the names Amberlite®, DOWEX®, PermutitQH®, Chempro® and Lewatite®. Polyperfluoroalkylene sulfonic acids, available under the name Nafion®, can also be used.
  • the ion exchangers used have an H+ ion capacity of 2 to 7 meq / g dry substance and an H2O content of 0.1 to 2% by weight.
  • molecular groups with SH function as cocatalyst can also be bound to the ion exchangers either directly on the matrix or via the sulfonic acid groups.
  • the modification of the acidic ion exchanger with mercapto-containing compounds is known (cf. EP-A 305 774, EP-A 023 325, DE-A 2 722 683).
  • the co-catalyst containing mercapto groups can also be used as a low molecular weight compound in unbound form e.g. as ⁇ -mercaptopropionic acid, n-alkyl mercaptan, are added to the reaction mixture.
  • the cocatalyst is used in amounts of 0.001-0.2 mol per mol of cyclohexanone of the formula (II).
  • the process according to the invention can be carried out continuously or batchwise, with the continuous procedure being preferred.
  • the acidic ion exchanger is filled into a suitable reactor, for example a vertical tubular reactor designed as a fixed bed, and the reaction mixture flows through it.
  • the flow rate of the reactants is adjusted so that the desired cyclohexanone conversion is achieved.
  • the reaction temperature is 20 to 150 ° C. Temperatures of 35 to 100 ° C are preferred. In the continuous procedure, the reaction temperature must be selected so that the bisphenol formed does not crystallize out in the reaction mixture in the exchanger bed.
  • the reaction can also be carried out in an inert solvent.
  • suitable solvents are toluene, chlorobenzene, methylene chloride, cyclohexane, dichloroethane, dioxane.
  • the addition of inert solvents is advantageous if the cyclohexylidene bisphenol formed is to be kept in solution at low temperatures.
  • the inert solvents can optionally also serve as entrainer for the water formed during the reaction during the reaction.
  • the cyclohexylidene bisphenols can be isolated by the process of the invention in various ways.
  • the reaction mixture is separated from the insoluble ion exchange resin by filtration at a temperature at which the cyclohexylidene bisphenol is dissolved in the reaction mixture.
  • the filtrate is then cooled and / or excess phenol is removed.
  • the resulting cyclohexylidene bisphenol-phenol adduct is filtered and can be purified by distillation, the pure cyclohexylidene bisphenol remaining and a dry phenol distillate being obtained which can be returned to the reaction mixture.
  • the cyclohexylidenebisphenol-phenol adduct can also be cleaved with water and / or a solvent in which the phenol is soluble and the bisphenol is largely insoluble.
  • Suitable solvents for this are aliphatic and aromatic hydrocarbons, for example hexane, cyclohexane, toluene, petroleum ether, chlorobenzene.
  • the cyclohexylidene bisphenols can also be isolated by adding a solvent to the reaction solution separated from the ion exchange resin, the cyclohexylidene bisphenol or the cyclohexylidene bisphenol-phenol adduct precipitating and being able to be filtered.
  • Suitable solvents for this are aliphatic and aromatic hydrocarbons such as hexane, pentane, petroleum ether, toluene, chlorobenzene.
  • the batch can be worked up by adding a solvent which dissolves the cyclohexylidene bisphenol and / or its phenol adduct at low temperatures.
  • Suitable solvents for this are aliphatic and aromatic ethers, esters and alcohols such as diisopropyl ether, dioxane, tetrahydrofuran, methyl acetate, methanol, ethanol, isopropanol.
  • the reaction product solution is filtered off from the ion exchanger and concentrated. To remove the excess phenol, extraction with water or steam distillation can be carried out.
  • Another effective method for removing excess phenol is to add a solvent to the concentrated reaction product solutions in which the phenol is dissolved and the desired cyclohexylidene bisphenol is largely undissolved.
  • the desired cyclohexylidene bisphenol can be isolated from the filtered reaction product solution via the formation of the cyclohexylidene bisphenol-phenol adduct as described above.
  • a mixture of 24 moles of phenol and 1 mole of 4-tert-butylcyclohexanone was continuously pumped through a vertically arranged 1 m long glass column with an inner diameter of 8 cm.
  • the glass column was filled with 660 cm3 of phenol-moist ion exchange resin, the acidic SO3H groups of which were 20% neutralized with 2-mercaptoethylamine.
  • a sulfonated styrene-divinylbenzene copolymer (type Lewatit SC 102 / H®) with 5 meq acid equivalents per gram of dry substance was used as the acidic cation exchange resin, which was predried by washing with phenol and then with toluene in vacuo to one Water content of 0.5% was dried (dry weight 250 g). The column temperature was 80-85 ° C. With a throughput of 180 g / h, a ketone conversion of 98% was obtained. The selectivity of 1,1-bis (4-hydroxyphenyl) -4-tert-butylcyclohexane was 84%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Claims (1)

  1. Procédé de préparation de cyclohexylidènebisphénols substitués de formule (I) :
    Figure imgb0012
     dans laquelle
    R¹ et R² représentent chacun, indépendamment l'un de l'autre, l'hydrogène, un halogène, de préférence le chlore ou le brome, un groupe alkyle en C₁-C₈, cycloalkyle en C₅-C₆, aryle en C₆-C₁₀, de préférence phényle, ou aralkyle en C₇-C₁₂, de préférence phényl-alkyle en C₁-C₄, plus spécialement benzyle,
    R³ représente un radical hydrocarboné en C₁-C₁₂ et
    n est égal à 1 ou 2, sous réserve que les substitutions géminales sont exclues,
    par réaction de phénols de formule (II) :
    Figure imgb0013
     dans laquelle
    R¹ et R² ont les significations indiquées en référence à la formule (I),
    en présence de catalyseurs de condensation acides, anhydres, et en présence de dérivés organiques du soufre servant de catalyseurs auxiliaires, avec des cyclohexanones de formule (III) :
    Figure imgb0014
     dans laquelle
    R³ et n ont les significations indiquées en référence à la formule (I),
    caractérisé en ce que l'on utilise en tant que catalyseurs de condensation acides, anhydres, des résines styrène-divinylbenzène sulfonées, des polymères du styrène réticulés et sulfonés, des résines phénol-acide formaldéhyde sulfonique, et, en tant que catalyseur auxiliaire, en quantité de 0,001 à 0,2 mol/mole de cyclohexanone de formule (III), l'acide β-mercaptopropionique ou la 2-mercaptoéthylamine.
EP91116809A 1990-10-13 1991-10-02 Procédé pour la fabrication de cyclohexylidenebisphénols substitués Expired - Lifetime EP0481287B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4032595A DE4032595A1 (de) 1990-10-13 1990-10-13 Verfahren zur herstellung von substituierten cyclohexyliden-bisphenolen
DE4032595 1990-10-13

Publications (3)

Publication Number Publication Date
EP0481287A2 EP0481287A2 (fr) 1992-04-22
EP0481287A3 EP0481287A3 (en) 1993-05-12
EP0481287B1 true EP0481287B1 (fr) 1996-01-17

Family

ID=6416257

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91116809A Expired - Lifetime EP0481287B1 (fr) 1990-10-13 1991-10-02 Procédé pour la fabrication de cyclohexylidenebisphénols substitués

Country Status (4)

Country Link
EP (1) EP0481287B1 (fr)
JP (1) JPH04282334A (fr)
DE (2) DE4032595A1 (fr)
ES (1) ES2082081T3 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19539444A1 (de) * 1995-10-24 1997-04-30 Bayer Ag Verfahren zur Herstellung von Bisphenolen unter Verwendung neuer Cokatalysatoren
JP3774789B2 (ja) 1998-10-20 2006-05-17 本州化学工業株式会社 ３，３，５−トリメチルシクロヘキシリデンビスフェノール類の製造方法
US6255439B1 (en) * 2000-08-31 2001-07-03 General Electric Company 1,1-Bis(4-hydroxyphenyl)-3-alkylcyclohexanes, method for their preparation and polycarbonates prepared therefrom
JP4472923B2 (ja) 2000-09-11 2010-06-02 本州化学工業株式会社 １，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサンの製造方法
US7015365B2 (en) * 2003-12-19 2006-03-21 General Electric Company Methods for preparing cycloalkylidene bisphenols

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE695169A (fr) * 1966-03-09 1967-09-08
US3760006A (en) * 1970-03-06 1973-09-18 Dow Chemical Co Ion exchange catalysts for the preparation of bisphenols
DE3727641A1 (de) * 1987-08-19 1989-03-02 Bayer Ag Mit thiazolinen modifizierte ionenaustauscher
NO170326C (no) * 1988-08-12 1992-10-07 Bayer Ag Dihydroksydifenylcykloalkaner

Also Published As

Publication number Publication date
JPH04282334A (ja) 1992-10-07
DE4032595A1 (de) 1992-04-16
EP0481287A3 (en) 1993-05-12
EP0481287A2 (fr) 1992-04-22
DE59107281D1 (de) 1996-02-29
ES2082081T3 (es) 1996-03-16

Similar Documents

Publication Publication Date Title
US4400555A (en) Ion exchange catalyzed bisphenol synethesis
JP2520879B2 (ja) ビスフエノ−ルの製造方法
EP0583712B1 (fr) Procédé pour la préparation de bisphénols
US4391997A (en) Ion exchange catalyzed bisphenol process
EP0314007B1 (fr) Procédé de préparation de bisphénols aromates
US5698600A (en) Process for the production of bisphenols with the use of new cocatalysts
EP0305774B1 (fr) Echangeur d'ions modifié par des thiazolines
DE69502554T2 (de) Verfahren zur Herstellung von Bisphenol-A und Polysiloxan-Katalysator dafür
DE69637268T2 (de) Verfahren zur Herstellung von tris(Hydroxyphenyl)-Verbindungen
DE3877505T2 (de) Isomerisierungsverfahren der nebenprodukte in der bisphenolsynthese.
US5780690A (en) Bisphenol synthesis on modified ion-exchange resins using specially purified carbonyl compounds
EP0355513A2 (fr) Isomérisation ou homologisation de bisphénols
EP0481287B1 (fr) Procédé pour la fabrication de cyclohexylidenebisphénols substitués
DE4121791C2 (de) Verfahren zur Herstellung von substituierten Cycloalkylidenbisphenolen
EP0249102B1 (fr) Echangeurs d'ions modifiés par des mercaptoamines
DE69101796T2 (de) Verfahren zur Herstellung von Bisphenol A.
EP0358992A2 (fr) Procédé pour la fabrication de bis-phénols
KR20060130169A (ko) 이성질체 형성이 감소된 비스페놀 ａ의 제조
DE69900653T2 (de) Verfahren zur Herstellung von Säuregruppen enthaltenden Bisxylenolen
DE19536366A1 (de) Herstellung von 2,2'-Bis(4-hydroxyphenyl)propanen in Gegenwart sulfonat- und mercaptogruppenhaltiger Organopolysiloxane
EP0847975B1 (fr) Méthode de préparation et de purification du 1,1,1-tris(4-hydroxyphényl)éthane
EP1272449A1 (fr) Melange de substances contenant du bisphenol a
EP1132367B1 (fr) Procédé de préparation de la 2,3,5-triméthyl-p-benzoquinone
EP0567857B1 (fr) Synthèse de bisphénols sur des résines échangeurs d'ions modifiées en utilisant des composés carbonylés spécialement purifiés
DE10135012A1 (de) Verfahren zur Herstellung von Bisphenolen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE ES FR GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE DE ES FR GB IT NL

17P Request for examination filed

Effective date: 19930728

17Q First examination report despatched

Effective date: 19940824

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT NL

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 59107281

Country of ref document: DE

Date of ref document: 19960229

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2082081

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19960220

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20021002

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20021016

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031002

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20031002

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040630

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20050914

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051002

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20051004

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20051026

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20051031

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070501

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070501

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20070501

BERE Be: lapsed

Owner name: *BAYER A.G.

Effective date: 20061031

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20061003

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061003

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061031